Aliphatically modified rosin resin and tackified adhesive

ABSTRACT

Aliphatically modified rosin resins are prepared by reacting rosin esters with aliphatic monomers. These aliphatically modified rosin resins are compatible with metallocene catalyzed polyolefins and other aliphatic base polymers and are used as tackifiers in combination with metallocene catalyzed polyolefins and other aliphatic base polymers to form adhesive compositions for hot melt and pressure sensitive applications.

FIELD OF THE INVENTION

The present invention relates to: aliphatically modified rosin resinsand their method of production; the use of aliphatically modified resinsas tackifiers in adhesive compositions; and the adhesive compositionsproduced thereby.

BACKGROUND OF THE INVENTION

A need presently exists for improved tackifying resins for use inthermoplastic adhesives formed of metallocene catalyzed polyolefins andother aliphatic base polymers.

Until somewhat recently, hot melt adhesives (HMAs) formed of ethylenevinyl acetate (EVA) were predominantly used in the packaging industryand in other applications. However, the introduction of metallocenecatalyzed polyolefin elastomers in the late 1990s led to the developmentof new HMAs which are superior to the EVA-based adhesives in both theirmachineability and in their relative oxidation resistance and clarity.

Adhesives formed of metallocene catalyzed polyolefin elastomers andother aliphatic base polymers are used, for example, for packaging(e.g., case or carton sealing, flexible packaging, etc.), productassembly applications, and pressure sensitive applications. Themetallocene polymers can provide improved thermal stability at high andlow temperatures, improved processability, machineability, reducedcrystallinity, lower color, and lower molecular weight.

As with other hot melt and pressure sensitive polymer adhesivescompositions, the aliphatic polymer based adhesive formulations alsoinclude tackifying resins which increase the adhesion (i.e., the abilityof the adhesive to form a lasting bond) of the adhesive to thesubstrate. These tackifiers tend to have low molecular weights (relativeto the base polymer), as well as glass transition and softeningtemperatures above room temperature, which give the tackifiers uniqueamorphous properties. Tackifiers frequently account for a significantportion of the weight of a hot melt adhesive product as they cancomprise up to 50% or more of the total mass of the product.

Heretofore, rosin ester tackifiers or oligomers have been successfullyused to improve the adhesion properties of various polymer adhesivecompositions. Unfortunately, however, these rosin ester tackifiers havenot been compatible with metallocene catalyzed polyolefins and otheraliphatic base polymers. When blended with these polymers, the blendedsystem turns opaque white and forms separate microphases which separatevery quickly. Fundamentally, the use of rosin ester tackifiers inmetallocene polymer compositions has been limited due to the compositionand structure of the ester as well as the disproportionation reactionswhich occur when the rosin is heated to a temperature above 230° C.During the disproportionation step of the rosin, either thermally or inthe presence of a disproportionation catalyst, the isomers of rosinconvert from the typical abeitic, palustric, and neoabietic types tomore stable dehydroabietic isomers. These isomers, with their terminalfused aromatic ring structure increase the polarity of the resin whichfurthers the rosin esters incompatibility with the aliphatic basepolymer.

Consequently, heretofore, the tackifying resin materials used inmetallocene catalyzed polyolefin and other aliphatic base polymercompositions have been hydrogenated hydrocarbon tackifiers or oligomers.In comparison to rosin ester tackifiers, these hydrogenated hydrocarbonresins, when formulated into typical adhesives, have higher meltviscosities, and reduced formulation latitude. Moreover, and moreimportantly, the hydrogenated hydrocarbon resins have less robustadhesion characteristics as compared to rosin ester tackifiers whenevaluated in similar formulations.

Therefore, in view of the above, it will be apparent that a need existsfor: (a) an improved tackifying resin for metallocene catalyzedpolyolefins and other aliphatic base polymers; (b) a rosin estertackifier composition which is compatible with metallocene catalyzedpolyolefins and other aliphatic base polymers; and (c) an improvedmetallocene catalyzed polyolefin adhesive composition comprising the newrosin ester tackifier composition.

SUMMARY OF THE INVENTION

The present invention satisfies the needs and alleviates the problemsdiscussed above.

In one aspect, there is provided a method of producing an aliphaticallymodified rosin resin. In another aspect, there is provided analiphatically modified rosin resin product produced by the inventivemethod. The method preferably comprises the steps of: (a) esterifyingrosin by reaction with a polyol to produce a rosin polyol ester and (b)reacting the rosin polyol ester with a monomer material to produce thealiphatically modified rosin resin. The monomer material is preferablyselected from: C₆ to C₂₂ alpha-olefins; vinyl-terminated monomers; C₆ toC₂₂ alpha-beta unsaturated esters and acids; fumaric, maleic, or acrylicesters or diesters of C₄ to C₂₂ aliphatic chains or rings; andcombinations thereof.

In another aspect, there is provided a thermoplastic adhesivecomposition comprising: an aliphatic base polymer material, a waxydiluent, and an aliphatically modified rosin resin. The aliphaticallymodified rosin resin is preferably produced by (a) esterifying rosin byreaction with a polyol to produce a rosin polyol ester and (b) reactingthe rosin polyol ester with a monomer material to produce thealiphatically modified rosin resin. The monomer material is preferablyselected from: C₆ to C₂₂ alpha-olefins; vinyl-terminated monomers; C₆ toC₂₂ alpha-beta unsaturated esters and acids; fumaric, maleic, or acrylicesters or diesters of C₄ to C₂₂ aliphatic chains or rings; andcombinations thereof.

In yet another aspect there is provided a thermoplastic adhesivecomposition comprising: a metallocene catalyzed polyolefin and analiphatically modified rosin resin. The aliphatically modified rosinresin is preferably produced by (a) esterifying rosin by reaction with apolyol to produce a rosin polyol ester and (b) reacting the rosin polyolester with 1-decene or vinyl monomers, or other depending on theexamples included.

Further aspects, features, and advantages of the present invention willbe apparent to those of ordinary skill in the art upon reading thefollowing Detailed Description of the Preferred Embodiments.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides an aliphatically modified rosin resintackifier which is compatible with metallocene catalyzed polyolefins andother aliphatic base polymer materials. In addition, the presentinvention provides a method of producing the inventive aliphaticallymodified rosin resin tackifier. Further, the present invention providesa thermoplastic adhesive composition which preferably comprises: (a) ametallocene catalyzed polyolefin or other aliphatic base polymermaterial; (b) the inventive aliphatically modified rosin resintackifier; and (c) a waxy diluent.

The inventive aliphatically modified rosin resin is preferably producedby a method comprising the steps of: (1) esterifying crude or othernon-functionalized rosin by reaction with a polyol to produce a rosinpolyol ester; (2) reacting the rosin polyolester with one or moremonomer materials to produce the inventive aliphatically modified rosinresin; and (3) also preferably vacuum stripping the aliphaticallymodified rosin resin product to remove unreacted monomer and to therebyalso typically increase the softening point of the inventivealiphatically modified rosin resin.

Alternatively, the inventive aliphatically modified rosin resin may beproduced by the method comprising the steps of: 1) reacting rosin withone or more monomer materials in the presence of a catalyst such asBentonite clay (F-100) or other catalyst which will assist with similarreaction pathways; 2) removing the catalyst via filtration and removingexcess monomer via either atmospheric or vacuum distillation; and 3)esterifying the modified rosin by reaction with glycerin or other polyolto produce the inventive aliphatically modified rosin resin

Many different polyols are known and used in the art to react with thecarboxylic core of the rosin structure thus producing rosin esters. Someexamples of said polyols include, but are not limited to:triethyleneglycol, diethyleneglycol, pentaerythritol, glycerol,sorbitol, trimethanolpropane, 1,4-cyclohexane dimethanol,1,4-butanediol, 1,3-propanediol, and ethylene glycol used solely or as acombination thereof.

Esterification catalysts and stabilizers for rosin esters are known inthe art. An example of an esterification catalyst preferred for use inthe inventive method is phosphonic acid,P-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]-, monoethylester, calcium salt (2:1). This composition is commercially availablefrom Mayzo under the name BNX 1425. The esterification catalyst willpreferably be present in the reaction mixture in amount in the range offrom about 0.04 to about 0.4% by weight of the total mixture.

Examples of monomer materials suitable for use in the second step of theinventive method for aliphatically modifying the previously producedrosin glycerin ester include, but are not limited to: branched, cyclic,and straight chained C₆ to C₂₂ alpha-olefins; vinyl-terminated monomers;C₆ to C₂₂ alpha-beta unsaturated esters and acids; fumaric, maleic, oracrylic esters or diesters of C₄ to C₂₂ aliphatic chains or rings; andcombinations thereof.

Examples of vinyl-terminated monomers preferred for use in the inventivemethod include, but are not limited to: branched, cyclic, or straightchained C₆ to C₂₂ vinyl ethers; ethyl vinyl ether; isobutyl vinyl ether;n-butyl vinyl ether; tert-butyl vinyl ether; cyclohexyl vinyl ether;dodecyl vinyl ether; octadecyl vinyl ether; or 2-ethyl hexyl vinylether. The vinyl-terminated monomers most preferred for use in theinventive method are: branched, cyclic, or straight chained C₆ to C₂₂vinyl ethers; cyclohexyl vinyl ether; dodecyl vinyl ether; octadecylvinyl ether; or 2-ethyl hexyl vinyl ether.

The C₆ to C₂₂ alpha-olefins preferred for use in the inventive methodare branched, cyclic, or straight chained C₁₀ to C₁₈ alpha-olefins. Thealpha-olefin most preferred for use in the inventive method is 1-decene.

When the aliphatic modification step of the inventive reaction method iscomplete or substantially complete, but before vacuum stripping, anantioxidant is preferably added to the reaction mixture. An example of asuitable antioxidant additive is pentaerythritoltetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate). Thisantioxidant is commercially available, from Irganox under the nameINGANOX 1010 and will preferably be used in the inventive method in anamount in the range of from about 0.05% to about 0.4% by weight of thetotal reaction mixture.

The chemical structure of the inventive aliphatically modified rosinresin produced by the inventive reaction method is presently unknown. Itis possible that the reaction which occurs between aliphatic monomer andthe rosin polyol ester in the second step of the inventive method is aDiels Alder reaction wherein the monomer acts as a dienophile.Alternatively, it is possible the aliphatic monomer may instead bereacting with the carboxylate group of the rosin polyol ester orpossibly with the dehydroabeitic acid isomers through a Friedel-Craftstype mechanism especially in the presence of a suitable catalyst such asZeolite or other suitable Friedel-Crafts catalyst.

As mentioned above, the thermoplastic adhesive composition provided bythe present invention preferably comprises: (b) one or more metallocenecatalyzed polyolefins and/or other aliphatic base polymer materials; (b)the inventive aliphatically modified rosin resin tackifier; and (c) awaxy diluent (e.g., a Fischer-Tropsch wax or other diluent of the typeused in the art for preparing hot melt or pressure sensitivethermoplastic adhesives). The metallocene catalyzed polyolefin or otheraliphatic base polymer material is preferably present in the inventiveadhesive composition in an amount in the range of from about 80 to about40 parts by weight and is more preferably present in an amount in therange of from about 55 to about 40 parts by weight. The inventivealiphatically modified rosin resin tackifier is preferably present inthe inventive adhesive composition in an amount in the range of fromabout 20 to about 60 parts by weight and is more preferably present inan amount in the range of from about 45 to about 60 parts by weight.

In addition to metallocene catalyzed polyolefins, examples of otheraliphatic base polymer materials suitable for use in the inventivethermoplastic adhesive composition include, but are not limited to:amorphous poly alpha olefins, polybutene polymers, atacticpolypropylene, polyethylene resins, hydrogenated rubber polymers, or acombination thereof.

The base polymer material used in forming the inventive thermoplasticadhesive composition will preferably be one or more metallocenecatalyzed polyolefins. The metallocene catalyzed polyolefin(s) can beany metallocene catalyzed polyolefin product(s) known for or otherwisesuitable for use in thermoplastic adhesive applications. Examples ofsuch metallocene catalyzed polyolefin products include, but are notlimited to, AFFINITY polyolefins and ENGAGE polyolefins which areavailable from Dow Chemical, Vistamaxx from ExxonMobil, and LICOCENEwhich is available from Clariant.

By way of example, but not by way of limitation, the inventivethermoplastic adhesive composition can be prepared by adding thecomposition components, preferably one at a time, to a heated mixingvessel, preferably with a full sized agitator, under a nitrogenatmosphere. Preferably, the waxy diluent will be added to the mixingvessel first, followed by the inventive aliphatically modified rosinresin tackifier (which has preferably been vacuum stripped) and then bythe metallocene catalyzed polyolefin(s) and/or other aliphatic basepolymer(s).

The components of the inventive adhesive composition will preferably bemixed until a smooth, clear, homogeneous blend is formed. The materialcan then, for example, be removed from the mixing vessel and extruded orotherwise processed to form chips or pellets. These product chips orpellets can be used, for example, in hot melt adhesive applications byadding the chips or pellets to a hot melting tank and pumping the meltedproduct through a nozzle for application of the material to the surfaceof any type of article, item or structure. The surface of a secondarticle, item, or structure is then pressed against or otherwise appliedthe treated surface of the first article to thereby bond the secondarticle to the first article.

Although the chemical structure of the aliphatically modified rosinresin product provided by the present invention has not yet beendetermined, the inventive product, as formed by the inventive productionmethod, is highly compatible with metallocene catalyzed polyolefins andother aliphatic base polymers to produce stable, smooth, and clearcompositions wherein phase separation does not occur. As compared to thetackifiers used heretofore with metallocene catalyzed polyolefins, theinventive aliphatically modified rosin resin also provides lower meltviscosities, higher specific adhesion properties, and better heatresistance.

Moreover, these results for the inventive aliphatically modified rosinresin are surprising and unexpected. To our knowledge, these are thefirst rosin ester based compounds which have been discovered to becompatible with metallocene catalyzed polyolefins. Typical rosin estertackifiers are not compatible with metallocene catalyzed polyolefins.Nor are blends comprising the prior rosin ester tackifiers mixed withalpha-olefins. To our knowledge, prior efforts to add hydrocarbons torosin ester tackifiers to produce products which would be compatiblewith metallocene catalyzed polyolefins also have not been successful.

The following examples are intended to illustrate, but in no way limit,the invention as claimed.

Example 1

To a 3 L four-neck round bottom flask equipped with an air drivenagitator, condenser, nitrogen sparge tube, and thermocouple was addedMWV rosin (1418.72 g, 4.68 mol). The solid rosin was heated to 180° C.under a nitrogen blanket to melt followed by the addition of Irganox1425 (5.6 g, 0.008 mol) and Lowinox TBM-6 (4.48 g, 0.013 mol). Afterheating to 200° C., glycerin (167.2 g, 1.82 mol) was added. The mixturewas heated to 270° C. over 4 h and stirred with a nitrogen sparge untilan acid number value of 15 mg KOH/g or below was reached. Thetemperature was decreased to 180° C. and Irganox® 1010 (4.0 g, 0.003mol) was added. After stirring for 5 min the mixture was poured toprovide resin product with typical properties such as Gardner color of 4(neat), acid number value of <11, and softening point of 86° C.

Example 2

To a 5 L four-neck round bottom flask equipped with an air drivenagitator, condenser, nitrogen sparge tube, and thermocouple was addedMWV rosin (2674.2 g, 8.83 mol). The solid rosin was heated to 180° C. tomelt followed by the addition of BNX® 1425 (10.79 g, 0.016 mol) andglycerin (315 g, 3.42 mol). The mixture was heated to 275° C. over 2 hand nitrogen sparging was initiated. The reaction was stirred for anadditional 4.5 h with nitrogen sparging before it was cooled to 180° C.and poured to provide a resin with a Gardner color of 4.7 (neat), anacid number value of 6.3 mg KOH/g, and a softening point of 90° C.

The glycerin ester resin (249.38 g) was placed in a 500 mL round bottomflask equipped with an air driven agitator, condenser, distillationtrap, nitrogen sparge tube, and thermocouple. The ester was heated to250° C. and Irganox® 1010 (0.65 g, 0.0006 mol) was added. Vacuum (−800mbar) was applied and the mixture was stirred for 1 h with a slightnitrogen sparge. The temperature was increased to 275° C. and held foran additional 40 min before cooling to 180° C. The resin was poured toprovide a resin product with a Gardner color of 4.9 (neat), an acidnumber value of 3 mg KOH/g, and a softening point of 93.3° C.

Example 3

To a 3 L four-neck round bottom flask equipped with an air drivenagitator, condenser, nitrogen sparge tube, and thermocouple was addedMWV rosin (1157.3 g, 3.82 mol). The solid rosin was heated to 180° C. tomelt followed by the addition of BNX® 1425 (4.66 g, 0.007 mol), andglycerin (136.32 g, 1.48 mol). The mixture was heated to 250° C. andstirred with a nitrogen sparge for 2 h. The temperature was increased to275° C. and the mixture was stirred for an additional 4 h with anitrogen sparge. The reaction was cooled to 180° C. and held overnightunder a nitrogen blanket.

Acid number analysis the next day revealed a value of 11 mg KOH/g. Thetemperature of the molten mixture was reduced to 170° C. and 1-decene(297.3 g, 2.12 mol) was added. After the solution was stirred at 170° C.for five hours, Irganox® 1010 (3.2 g) was added and the temperature wasgradually increased to 220° C. to remove excess 1-decene. The resin wascooled to 180° C. and poured. To ensure all excess 1-decene was removedthe solid was re-melted at 220° C. and vacuum was applied (−956 mbarvacuum). The molten resin was gradually heated to 240° C. under vacuum(−956 mbar) and stripped until no further distillation was observed(typically 1 h total time under vacuum). The mixture was cooled to 180°C. and released from vacuum with nitrogen. The resin was poured andcooled to provide the inventive product with a Gardner color of 5.6(neat), an acid number value of 7 mg KOH/g, and a softening point of89.6° C.

Example 4

To a 1 L four-neck round bottom flask equipped with an air drivenagitator, condenser, nitrogen sparge tube, and thermocouple was addedMWV rosin (400 g, 1.32 mol). The solid rosin was heated to 180° C. tomelt and 1-decene (200 g, 1.43 mol) was added. Bentonite clay (F-100)(16 g) was added and the suspension was stirred at 170° C. for 1.5 hbefore heating to 180° C. and stirring an additional 3.5 h. The reactionwas cooled to 160° C. and held overnight. The next day, the temperaturewas increased to 180° C. and stirring was continued for an additional6.5 h. The mixture was poured into a tin pan and allowed to cool. Thedark residue was dissolved in toluene (200 mL) at 100° C. The solutionwas cooled to 50° C. and filtered through a bed of Celite® using toluene(50 mL) to wash the Celite® bed. The slightly hazy solution was filteredthrough whattman #2 filter paper to provide a clear solution. Thetoluene and excess 1-decene were removed via atmospheric distillation(maximum temperature at 250° C.) and the resultant resin was poured tocool. 319 g of modifiedrosin was isolated with an acid number value of145 mg KOH/g and a softening point of 58° C.

300.79 g of the modified rosin was placed in a 500 mL four-neck roundbottom flask equipped with an air driven agitator, condenser, nitrogensparge tube, and thermocouple. The temperature was increased to 180° C.to melt the resin. To the molten mixture was added BNX® 1425 (1.14 g,0.002 mol), Rosinox™ (0.65 g), and glycerin (21.61 g, 0.23 mol). Themixture was heated to 250° C. with a nitrogen sparge for 3.5 h and thenthe temperature was increased to 275° C. for an additional 2 h beforecooling to 180° C. for overnight holding.

The next day, additional glycerin (10.8 g, 0.12 mol) was added and themixture was heated to 250° C. After stirring for 4.5 h at 250° C. with anitrogen sparge, the resin was cooled to 180° C. Irganox® 1010 (0.79 g,0.0007 mol) was added and the mixture was stirred for 10 min. The resinwas poured and cooled to provide the inventive product with an acidnumber value of 8.7 mg KOH/g, and a softening point of 80° C.

Compatibility Analysis Via Visual Clarity for Metallocene CompatibleTackifiers

Compatibility of Rosin-based tackifiers with Metallocene catalyzedpolymers for adhesive applications has long been questioned. Judging therelative or absolute compatibility can be performed by characterizingthe relative initial and aged melt clarity of a formulation at standardtemperature (350° F.). This test protocol used molten optical clarity,in a manner similar to an ink or coating being applied and dried overLaneta paper. In the case of an ink or paint, the relative hiding power(the opposite of clarity) is characterized. In this determination, weobserve and rate the clarity of the molten subject against multiplebackgrounds, assigning a ranking for clarity against an indigo bluebackground, a medium purple background with white block print letteringand a white background with fine lined black characters.

This was a timed evaluation that required a minimum of 96 hours, withdaily observations at 24 hour intervals. It was recommended that thistesting begin on a Monday morning, which allowed for completion of theobservation without incurring weekend work time. All Hot Melt adhesiveformulas to be tested were prepared in advance, under standardconditions with standard equipment, or as required. Upon completion ofthe batch, 60 mL test tube was filled with 45 to 50 grams orapproximately one inch below the top of the test tube. This allowedspace for the silicone stopper to be placed, and also provided forapproximately ¼ inch of head space.

Test Tube Filling Protocol Used when not Making a Batch:

-   -   1. Heat all samples to be tested in a 350 F oven. Heat for at        least one hour; possibly longer if there are more than three        samples to be evaluated.    -   2. Place a clean 60 mL glass test tube in a narrow mouth jar,        allowing it to stand as upright as possible.    -   3. Mark either the test tube or jar, to identify each sample.    -   4. Pour one sample, heated to 350° F. in a metal paint can, into        a 60 mL glass test tube. Repeat for each sample.    -   5. Fill with approximately 45 to 50 grams of material, or enough        until the level of material is approximately 1 inch from the        top.    -   6. Immediately stopper the test tube. There should now be        approximately ¼ to ½ inch head space in the sealed test tube.    -   7. Place the test tube & jar into a pre-heated oven and allow to        heat for one hour.

Color Determination Protocol Used:

-   -   1. Orient the background to form a 90 degree angle to the work        surface upon which it is rested. Position the background so that        the dark blue colored portion is closest to the work surface and        the white portion is the furthest away from the work surface.    -   2. After all samples are fully molten, remove one sample at a        time, gripping with either small tongs and/or a heat resistant        glove; and immediately rest against our color backdrop    -   3. Place test tube as close to the color backdrop as possible        and IMMEDIATELY:    -   4. Assess the clarity via the following criterion.        -   a. If the dark blue color is clearly visible, rate the            sample as at least a 1.0 and continue with b below            -   i. If the blue color is not clearly visible rate the                sample a 1.0 and suspend the evaluation.        -   b. Immediately assess the clarity against the purple            background. If the white lettering is visible, rate the            sample as a 2.0 and continue to c below            -   i. If the purple color and white lettering is NOT                visible, rate the sample as a 2.0- and return to the                oven.        -   c. Immediately assess the clarity against the white            background with black lettering. If the lettering is            visible, rate the sample as a 3.0.            -   i. If the white color and black lettering are visible                but not distinguishable, rate the sample as a 3.0—and                proceed to #4 below.    -   5. After each sample has been characterized, put each sample        back into the oven and repeat the evaluation every 24 hours,        until 96 hours have passed.    -   6. NOTE: Each sample can be rated as a “+”, in addition to their        numerical grade, if it displays exceptional clarity in which the        script (either block white or fine lined black) is VERY clearly        legible.

The viscosity of each adhesive was taken using a DV-I Prime BrookfieldViscometer and thermosel with a #27-spindle. Viscosity was reported incentipoise (CPS). Viscosities were recorded at 350° F. Mettler DroppingPoint was determined using a DP-90 Dropping Point unit.

PAFT (Peel Adhesion Failure Temperature) and SAFT (Shear AdhesionFailure Temperature) values were generated using 40 lb Kraft recycledpaper as the test substrate. The bonded area was 1″×1″ and the adhesivefilm thickness was approximately 18-20 mils. 100 gram weights were usedfor the PAFT and SAFT testing. Five samples of each were tested and thefailure temperatures were averaged. The samples were run in an ovenprogrammed to increase 1° C. per minute from a starting temperature of40° C.

Open Time and Set Speed comparisons were conducted by heat reactivating18-20 mil films of the adhesive at 350° F. for two minutes. A film ofeach adhesive was placed 2.5 inches apart on 20 lb. bond paper attachedto a backing board and heated at 350° F. for 2 minutes. After twominutes the samples were taken out of the oven and another piece of 20lb. bond paper was placed on the molten adhesive surface and compressionwas provided with a roller that weighed 4946 grams. Once compressed, thetop paper was peeled back against itself. Open time was observed whenthe adhesive material ceased to transfer and Set Speed was noted whenthe paper fiber was torn.

Adhesion (bonding) was tested using a Rock-Tenn Bond Simulator to applyan approximately ⅛″ wide bead to the surface of a substrate at 350° F.The glue gun pressure was 55 PSI. The glue tank pressure was 50 PSI. Themachine speed was 100 ft/min and the dwell time was 1 second before 0.5seconds of compression at 10 PSI. The samples were exposed to varioustemperatures overnight and then pulled apart at the exposuretemperature. Fiber tear was recorded. Five samples were tested for eachcondition and the average fiber tear was reported. Fiber tear wasgenerated by physically debonding the samples and observing thepercentage of fiber tear along the glue line.

The paper substrates used in the adhesion (bonding) tests were:

-   -   Carrier Kote®: an unbleached, coated kraft paperboard which        remains strong when wet.    -   99% recycled corrugated board.    -   Printkote®: a bright white, glossy paperboard designed to        laminate to single-faced corrugated board.    -   Nomar® 70AFN: a water based, non-abrasive coating generally used        to provide abrasion protection for gas flushed food packaging or        small appliances.

TABLE 1 Formulas for Resin/Polymer Compatibility Testing Formulas ForResin-Polymer Compatibility Testing Trade Adhesive Sample ID RawMaterial Name 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Hydrogenated Eastotac 4030 30 Hydrocarbon H-100 W Control Hydrogenated Escorez 40 30 30 DCPDControl 5400 Example 1 Example 1 40 30 Resin Example 2 Example 2 40 30Resin Example 3 Example 3 40 30 Resin Example 4 Example 4 40 30 ResinMetallocene Affinity 40 40 40 40 40 40 Catalyzed GA 1900 PolyolefinElastomer Polyethylene Epolene 60 60 60 60 Homopolymer C-10 MetalloceneLicocene 70 70 70 70 Catalyzed PP 1502 Propylene- Ethylene- copolymerFischser Sasolwax 20 20 20 20 20 20 10 10 10 10 Tropsch Wax H-1 Total100 100 100 100 100 100 100 100 100 100 100 100 100 100

TABLE 2 Resin Polymer Compatibility Testing Results Resin-PolymerCompatibility Testing Results Reheated Clarity Scale (1 to 3) Reheatedand Kept at 350° F. Sample 60 24 48 72 96 ID Test Resin Base PolymerMinutes Hours Hours Hours Hours 1 Hydrogenated Metallocene 3+ 3+ 3+ 3+3+ Hydrocarbon Catalyzed Control Polyolefin Elastomer 2 HydrogenatedMetallocene 3+ 3+ 3+ 3+ 3+ DCPD Control Catalyzed Polyolefin Elastomer 3Example 1 Metallocene 2− 2− 2− Test Test Catalyzed Stopped StoppedPolyolefin Elastomer 4 Example 2 Metallocene 2 2 2− Test Test CatalyzedStopped Stopped Polyolefin Elastomer 5 Example 3 Metallocene 3 3 3+ 3+3+ Catalyzed Polyolefin Elastomer 6 Example 4 Metallocene 3+ 3+ 3+ 3+ 3+Catalyzed Polyolefin Elastomer 7 Hydrogenated Polyethylene 3+ 3+ 3+ 3+3+ Hydrocarbon Homopolymer Control 8 Hydrogenated Polyethylene 3+ 3+ 3+3+ 3 DCPD Control Homopolymer 9 Example 3 Polyethylene 3+ 3+ 3+ 3+ 3+Homopolymer 10 Example 4 Polyethylene 3+ 3+ 3− 3− 3− Homopolymer 11Hydrogenated Metallocene 3+ 3+ 3+ 3+ 3+ Hydrocarbon Catalyzed ControlPropylene- Ethylene- copolymer 12 Hydrogenated Metallocene 3+ 3+ 3− 3−3− DCPD Control Catalyzed Propylene- Ethylene- copolymer 13 Example 3Metallocene 3 3− 3− 3− 3− Catalyzed Propylene- Ethylene- copolymer 14Example 4 Metallocene 3+ 3+ 3+ 3+ 3+ Catalyzed Propylene- Ethylene-copolymer

TABLE 3 Adhesive Formulations for Performance Testing AdhesiveFormulations For Performance Testing C5 C5 Hydrocarbon Example 3 Example4 Hydrocarbon Example 3 Example 4 Sample Control Adhesive AdhesiveControl Adhesive Adhesive ID Adhesive #1 #1 #1 Adhesive #2 #2 #2Affinity 21 21 21 22 22 22 AG-1900 Affinity 21 21 21 20 20 20 AG-1950Sasolwax 20 20 20 20 20 20 H-1 Irganox 0.5 0.5 0.5 0.5 0.5 0.5 1010Escorez 27.5 27.5 27.5 5637 Eastotack 10 37.5 H-100 W Example 10 37.5 3Resin Example 10 37.5 4 Resin Total 100 100 100 100 100 100

TABLE 4 Performance Testing Performance Testing C5 C5 HydrocarbonExample 3 Example 4 Hydrocarbon Example 3 Example 4 Control AdhesiveAdhesive Control Adhesive Adhesive Sample ID Adhesive #1 #1 #1 Adhesive#2 #2 #2 HC Resin NA-Control 21.50% 21.50% NA-Control 100% 100%Replacement Level Viscosity (CPS) @350° F. 1,015 1,115 1,095 927 815 835Batch Information Color (Gardner) −0.4 3.1 3.8 −0.4 4.1 5 SofteningPoint 106.9 108 107.3 106.1 107.2 107.4 (° C.) Heat Resistance (° F.)PAFT 160 158 160 135 131 134 SAFT 226 228 228 221 223 225 Tack Down(Rate of Set) Open Time Control Longer Similar Control Similar SimilarSet Speed Control Slightly Similar Control Similar Similar SlowerThe viscosities of the inventive adhesive test formulations werecomparable. All formulations fell within the typical range for a generalpurpose packaging adhesive. Also, the open time and set speed of theinventive formulations were consistent with one another and weresuitable for many packaging applications. Further, the inventive resinswhich include Example 3 Adhesive. #1 through Example 3 Adhesive#2offered PAFT heat resistance and SAFT shear adhesion failuretemperatures which were in line with the hydrocarbon control.

TABLE 5 Adhesion Testing (% Fiber Tear) Adhesion Testing (% Fiber Tear)C5 C5 Hydrocarbon Example 3 Example 4 Hydrocarbon Example 3 Example 4Control Adhesive Adhesive Control Adhesive Adhesive Sample ID Adhesive#1 #1 #1 Adhesive #2 #2 #2 HC Resin NA-Control 21.50% 21.50% NA-Control100% 100% Replacement Level 99% Recycled 100 100 100 100 100 100Corrugate Carrier Kote ® 100 100 100 100 100 100 Printkote ® 100 100 100100 100 100 Michelman Nomar 0 17 13 8 60 72 70The inventive resins in Example 3 and 4 showed equivalent performance tothe hydrocarbon control samples on 99% recycled corrugate and CarrierKote®.

Most importantly, on the more challenging Michelman Nomar 70 coatedcorrugate substrate, the inventive compositions of Example 3 and 4produced moderate levels of fiber tear whereas the control sampleproduced almost no adhesion or fiber tear, thus showing that thefunctionality of the inventive rosin resin provides enhanced adhesionperformance.

Thus, the present invention is well adapted to carry out the objects andattain the ends and advantages mentioned above as well as those inherenttherein. While presently preferred embodiments have been described forpurposes of this disclosure, numerous changes and modifications will beapparent to those of ordinary skill in the art. Such changes andmodifications are encompassed within this invention as defined by theclaims.

What is claimed is:
 1. A method of producing an aliphatically modifiedrosin resin comprising the steps of: esterifying a rosin by reactionwith a polyol to produce a rosin polyol ester and reacting said rosinpolyol ester with a monomer material to produce said aliphaticallymodified rosin resin, wherein said monomer material is selected from: C₆to C₂₂ alpha-olefins; vinyl-terminated monomers; C₆ to C₂₂ alpha-betaunsaturated esters and acids; fumaric, maleic, or acrylic esters ordiesters of C₄ to C₂₂ aliphatic chains or rings; and combinationsthereof.
 2. The method of claim 1 wherein said rosin is reacted withsaid polyol in step (a) in the presence of a catalyst effective for 4+2additions and other electrophilic substitutions.
 3. The method of claim2 wherein said catalyst is: Bentonite Clay (F-100).
 4. The method ofclaim 1 wherein said monomer material is a C₆ to C₂₂ alpha-olefin. 5.The method of claim 1 wherein said monomer material is 1-decene.
 6. Themethod of claim 1 wherein said monomer material is a branched, cyclic,or straight chained C₆ to C₂₂ vinyl ether.
 7. The method of claim 1wherein said monomer material is ethyl vinyl ether, isobutyl vinylether, n-butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinylether, dodecyl vinyl ether, octadecyl vinyl ether, or 2-ethyl hexylvinyl ether.
 8. An aliphatically modified rosin resin produced by themethod of claim
 1. 9. An aliphatically modified rosin resin produced bythe method of claim
 2. 10. An aliphatically modified rosin resinproduced by the method of claim
 3. 11. An aliphatically modified rosinresin produced by the method of claim
 4. 12. An aliphatically modifiedrosin resin produced by the method of claim
 5. 13. An aliphaticallymodified rosin resin produced by the method of claim
 6. 14. Analiphatically modified rosin resin produced by the method of claim 7.15. A thermoplastic adhesive composition comprising an aliphatic basepolymer material and an aliphatically modified rosin resin produced by(a) esterifying a rosin by reaction with a polyol to produce a rosinpolyol ester and (b) reacting said rosin polyol ester with a monomermaterial to produce said aliphatically modified rosin resin, whereinsaid monomer material is selected from: C₆ to C₂₂ alpha-olefins;vinyl-terminated monomers; C₆ to C₂₂ alpha-beta unsaturated esters andacids; fumaric, maleic, or acrylic esters or diesters of C₄ to C₂₂aliphatic chains or rings; and combinations thereof.
 16. Thethermoplastic adhesive composition of claim 15 wherein said aliphaticbase polymer material comprises one or more metallocene catalyzedpolyolefins, one or more amorphous poly alpha olefins, atacticpolypropylene, one or more polyethylene resins, one or more hydrogenatedrubber polymers, or a combination thereof.
 17. The thermoplasticadhesive composition of claim 16 wherein said aliphatic base polymermaterial is present in said thermoplastic adhesive composition in anamount of from about 40 to about 80 parts by weight and saidaliphatically modified rosin resin is present in said thermoplasticadhesive composition in an amount of from about 20 to about 60 parts byweight.
 18. A thermoplastic adhesive composition comprising ametallocene catalyzed polyolefin and an, aliphatically modified rosinresin produced by (a) esterifying a rosin by reaction with glycerin toproduce a rosin glycerin ester and (b) reacting said rosin glycerinester with 1-decene.
 19. The thermoplastic adhesive composition of claim18 wherein said rosin is reacted with said glycerin in the presence of acatalyst.
 20. The thermoplastic adhesive composition of claim 18 whereinsaid aliphatically modified rosin resin is a vacuum stripped rosinresin.
 21. The thermoplastic adhesive composition of claim 18 whereinsaid metallocene catalyzed polyolefin is present in said thermoplasticadhesive composition in an amount of from about 40 to about 80 parts byweight and said aliphatically modified rosin resin is present in saidthermoplastic adhesive composition in an amount of from about 20 toabout 60 parts by weight.